The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.     

Variability of retention process of isoxaflutole and its diketonitrile metabolite in soil under conventional and conservation tillage

BACKGROUND: Sorption largely controls pesticide fate in soils because it influences its availability for biodegradation or transport in the soil water. In this study, variability of sorption and desorption of isoxaflutole (IFT) and its active metabolite diketonitrile (DKN) was investigated under conventional and conservation tillage. RESULTS: According to soil samples, IFT K_D values ranged from 1.4 to 3.2 L kg^?1 and DKN K_D values ranged from 0.02 to 0.17 L kg^?1. Positive correlations were found between organic carbon content and IFT and DKN sorption. IFT and DKN sorption was higher under conservation than under conventional tillage owing to higher organic carbon content. Under conservation tillage, measurements on maize and oat residues collected from the soil surface showed a greater sorption of IFT on plant residues than on soil samples, with the highest sorbed quantities measured on maize residues (K_D ≈ 45 L kg^?1). Desorption of IFT was hysteretic, and, after five consecutive desorptions, between 72 and 89% of the sorbed IFT was desorbed from soil samples. For maize residues, desorption was weak (<50% of the sorbed IFT), but, after two complementary desorptions allowing for IFT hydrolysis, DKN was released from maize residues. CONCLUSION: Owing to an increase in organic carbon in topsoil layers, sorption of IFT and DKN was enhanced under conservation tillage. Greater sorption capacities under conservation tillage could help in decreasing DKN leaching to groundwater. Copyright © 2012 Society of Chemical Industry     

Movement of pesticides to surface waters from a heavy clay soil

A field experiment at Cockle Park, Northumberland on a clay loam soil (Dunkeswick series) cropped with winter wheat investigated the effects of drainage and season of application on pesticide movement. Isoproturon, mecoprop, fonofos and trifluralin were applied in two consecutive seasons at normal agricultural rates to three hydrologically isolated plots each of 0.25 ha. Two of the plots were mole-drained and the third was an undrained control. Surfacelayer flow and drainflow from each plot were monitored at 10-min intervals. Samples of flow were analysed for pesticides to evaluate transport of applied chemicals from the site. Despite widely differing properties (K_oc 20–8000 ml g^?1, t_1/2 10–60 days), all four pesticides were found in surface-layer flow and mole drainflow from the site. Maximum concentrations of pesticides in flow ranged from 0.1 to 121 μg litre^?1 (aqueous phase) and < 0.2 to 48 μg litre^?1 (particulate phase). Over two contrasting seasons, total losses of pesticides in flow followed total amounts of flow and were approximately four and five times larger, respectively, in 1990/91 than in 1989/90. The maximum loss occurred from the undrained plot and was 2.8 g isoproturon (0.45% of that applied). Total losses of autumn-applied pesticides from an undrained plot were up to four times greater than losses from a mole-drained plot. Mole drainage decreased movement of pesticides from this slowly permeable soil by reducing the amount of surfacelayer flow. Maximum concentrations of mecoprop and isoproturon in drainflow were 10–20 times larger following spring application than after application in autumn. Bypass flow down soil cracks was an important process by which pesticide was lost from the site, with transport to the drainage system via mole channels (55 cm depth) after less than 0.5 and 6.7 mm net drainage in the two winters.     

Fenbutatin oxide,fate in soil after extensive commercial use in Italy and Spain

The long-term fate of the acaricide, fenbutatin oxide, in soil has been investigated. Residues of the compound and its two principal metabolites have been determined in soil samples obtained from citrus orchards in Italy and Spain where the product had been applied commercially over a period of 6–10 years. The average fenbutatin oxide content in the upper 0–15 cm soil layer ranged from ? 1 mg kg^?1 to 5 mg kg^?1 in sites receiving single and double applications per year. The residues were located primarily (> 95%) in the top 0–30 cm layer and there was virtually no movement of the compound through the soil to lower depths. Below 0.5 m depths, the sites contained average concentrations of ? 0.01 mg kg^?1, the limit of determination. No significant build-up of residues was observed and the data indicate an approximate half-life in soil of just less than one year. Residues of the two metabolites, dihydroxy-bis(2-methyl-2-phenylpropyl)stan-nane and 2-methyl-2-phenylpropyl stannonic acid, were on average 11% and 16% of the fenbutatin oxide concentration, respectively. As with fenbutatin oxide, there was no significant movement through the soil to lower levels.     

Build-up and subsequent decline of residues of quintozene and hexachlorobenzene in lettuce in sequential crops

The build-up and decline of quintozene and hexachlorobenzene residues in protected lettuce, resulting from one to five treatments of the soil (each of 35 g m-2) with a quintozene formulation, have been studied. Residue levels were monitored in each experimental crop during growth until harvest. Residues in the soil at harvest were also determined. Quintozene residues in the harvested lettuce were in the range < 0.02–0.80 mg kg^?1 and those of hexachlorobenzene were in the range < 0.02–0.05 mg kg^?1 (expressed on a fresh weight basis). Residue levels in the soil were 5.4–231 mg kg^?1 for quintozene, and 0.20–5.4 mg kg^?1 for hexachlorobenzene (expressed on a dry weight basis). Under the experimental conditions of the trial there was no significant build-up of quintozene or hexachlorobenzene in harvested lettuce, even after five treatments to the same site.     

Fate of fluroxypyr in soil

Fluroxypyr-MHE (methylheptyl ester) was applied to small field plots containing Londo sandy loam soil. After 30 days, fluroxypyr had degraded to about 60% of the initial concentration, but was still the main component, while after 120 and 366 days the methoxypyridine metabolite was the main component in the soil. At 30, 120, and 366 days, lettuce, turnips, green beans, soybeans, and wheat were planted and grown with no observed injury. Residues of ¹⁴C in the edible crop fractions were indistinguishable from ¹⁴C in control plants exposed to ¹⁴CO₂, while residues in plant greens and chaff were low (0.1–0.2 mg kg^?1), with little evidence of fluroxypyr and no evidence of metabolite uptake. These results indicate that the methoxypyridine metabolite, if present in the soil, does not harm and is not taken up into the plants.     

Uptake of phorate by lettuce

Following experimental and commercial applications to soil of a granular formulalation of phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate), residues in the soil and in lettuce were determined by gas-liquid chromatography. When applied by the bow-wave method as a continuous logarithmically-changing dose ranging from approximately 0.9 to 16.0 kg a.i. ha^?1, the proportional rate of oxidation in soil of phorate sulphoxide to phorate sulphone was inversely related to dose. Ten weeks after application, total phorate residues in the soil had declined by about 35% at all dose levels. Residues in mature lettuce, from the 1-5 kg ha^?1 dose-range, comprised the parent and oxygen analogue sulphoxides and sulphones; the relative proportions of the individual metabolites were independent of dose. Over this dose-range, total residue concentrations in the crop became proportionally slightly greater with increasing dose. When single doses of 1.1, 2.0 or 2.2 kg a.i. ha^?1 were applied at drilling, the total residue concentrations in the lettuce declined from 5 mg kg^?1 in seedlings from some treatments to <0.05 mg kg^?1 at harvest. In plants raised in peat blocks containing 10 or 20 mg a.i. per block, however, residues in seedlings totalled 45-47 mg kg^?1 and declined to only 0.7 mg kg^?1 at harvest. It was concluded that bowwave applications of phorate when field-sowing lettuce were unlikely to lead to unacceptable residues in the harvested crop, but that residues in lettuce raised in phorate-treated peat blocks may be unacceptably high.     

The behavior of clomazone in the soil environment

BACKGROUND: Clomazone is a herbicide used to control broadleaf weeds and grasses. Clomazone use in agriculturally important crops and forests for weed control has increased and is a potential water contaminant given its high water solubility (1100 µg mL^?1). Soil sorption is an environmental fate parameter that may limit its movement to water systems. The authors used model rice and forest soils of California to test clomazone sorption affinity, capacity, desorption, interaction with soil organic matter and behavior with black carbon. RESULTS: Sorption of clomazone to the major organic matter fraction of soil, humic acid (HA) (K_d = 29–87 L kg^?1), was greater than to whole soils (K_d = 2.3–11 L kg^?1). Increased isotherm non‐linearity was observed for the whole soils (N = 0.831–0.893) when compared with the humic acids (N = 0.954–0.999). Desorption isotherm results showed hysteresis, which was greatest at the lowest solution concentration of 0.067 µg mL^?1 for all whole soils and HA extracts. Aliphatic carbon content appeared to contribute to increased isotherm linearity. CONCLUSION: The results indicate that clomazone does not sorb appreciably to sandy or clay soils. Its sorption affinity and capacity is greater in humic acid, and consequently clomazone has difficulty desorbing from soil organic matter. Sorption appears to follow processes explained by the dual‐mode model, the presence of fire residues (black carbon) and a recently proposed sorption mechanism. Copyright © 2009 Society of Chemical Industry     

Non-target effect of herbicides: I. effect of glyphosate and hexazinone on soil microbial activity. Microbial population,and in-vitro growth of ectomycorrhizal fungi

The effects of two herbicides, glyphosate (as a 359 g litre^?1 SL) and hexazinone (as a 50gkg^?1 granule) on soil microbial population, carbon dioxide evolution, and in-vitro growth of five species of ectomycorrhizal fungi were investigated. Glyphosate at 0–54 and 3.23 kg a.i. ha^?1 and hexazinone at 1. 2 and 8 kg a.i. ha^?1 did not reduce soil microbial population or carbon dioxide evolution in the long term (6 months). However, there was a significant short-term (2 months) effect of glyphosate on both fungal and bacterial counts at the 0.54 kg ha^?1 treatment. In in-vitro tests, Cenococcum graniforme. Hebeloma crustuliniforme and Laccaria laccata were more susceptible to both herbicides than was Suillus tomentosus. which was, in turn, more susceptible than Paxillus involutus. The growth of all five ectomycorrhizal fungi was significantly reduced when subjected to concentrations above 50 μl formulation litre^?1 (glyphosate) or 50 μg formulation litre^?1 (hexazinone).     

Grain protectants for the control of malathion-resistant insects in stored sorghum

Duplicate experiments were carried out on bulk sorghum stored in South Queensland and in Central Queensland. Bioassays of treated grain, conducted during 6 months' storage, established that fenitrothion (12 mg kg^?1)+ bioresmethrin (1 mg kg^?1), and pirimiphos-methyl (4 mg kg^?1)+ carbaryl (8 mg kg^?1), controlled typical malathionresistant strains of Sitophilus oryzae (L.), Rhyzopertha dominica (F.), Tribolium castaneum (Herbst), and Ephestia cautella (Walker). Chlorpyrifos-methyl (10 mg kg^?1)+ pyrethrins (1.5 mg kg^?1)+ piperonyl butoxide (12 mg kg^?1), and fenitrothion (12 mg kg^?1)+ (1R)-phenothrin (1 mg kg^?1), also controlled the strains of S. oryzae, T. castaneum and E. cautella, but were only partly effective against R. dominica. Methacrifos (15 mg kg^?1) controlled all the tested species except E. cautella. Chemical assays established that the residues and rates of breakdown of these grain protectants on sorghum conformed to the general pattern for other cereal grains; residues from the above treatments were below the individual Maximum Residue Limits recommended by the Codex Alimentarius Commission.     

Chlorpyrifos-methyl plus bioresmethrin; Methacrifos; Pirimiphos-methyl plus bioresmethrin; and synergised bioresmethrin as grain protectants for wheat

Field trials with various pesticide combinations were carried out on bulk wheat in commercial silos in Queensland, South Australia and Western Australia. Laboratory bioassays on samples of treated grain at intervals over 8 months using malathion-susceptible and malathion-resistant strains established the following orders of efficacy: against Sitophilus oryzae (L.), chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = methacrifos 15 mg kg^?1 in aerated storage > pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1 = bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1; against Rhyzopertha dominica (F.), bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1 > methacrifos 15 mg kg^?1 > chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1. All treatments completely prevented production of progeny in Sitophilus granarius (L.), Tribolium castaneum (Herbst), T. confusum Jackquelin du Val and Oryzaephilus surinamensis (L.). The biological efficacy of methacrifos was greater and the rate of degradation lower in aerated than in non-aerated storage. Residue levels of all compounds were determined chemically and were below proposed international residue levels to be considered by the Codex Alimentarius Commission.     

Control of Achillea millefolium L. (yarrow) by rotary cultivation and glyphosate

Various control strategies for Achillea millefolium L. (yarrow) were investigated in a dense stand of the weed at Lincoln College in 1977–1978. In early spring plots were either rotary cultivated or left undisturbed. In late spring, plots of both previous treatments were either left undisturbed, rotary cultivated or sprayed with glyphosate at 1·5 kg ha^?1. The whole experiment was rotary cultivated twice 1 week later and sown with Hordeum vulgure L. cv. Zephyr (barley) at 144 kg seed ha^?1. MCPA + dicamba at 0·9+0·15 kg ha^?1 was applied to half of each plot when the second node was detectable (Zadok 32). Rotary cultivation and glyphosate both substantially reduced the regrowth of A. millefolium but glyphosate reduced regrowth by a greater proportion when applied to undisturbed plants than when applied to plants regenerating after cultivation. Both gave a more than 95% reduction compared to the control (rotary cultivation only at sowing time) in the amount of A. millefolium present in the barley stubble in the autumn. MCPA + dicamba caused seedling mortality but did not affect the numbers of primary shoots from rhizome fragments. The grain yield of the barley increased from 2·91 t ha^?1 when A. millefolium was not controlled to 4·23 t ha^?1 with good control. The barley yield appeared to be restricted by competition from regenerating A. millefolium and by a nitrogen deficiency induced in some regimes by nitrogen immobilization in decaying rhizomes.     

Effects of repeated glyphosate applications on soil microbial community composition and the mineralization of glyphosate

Background: Repeated applications may have a greater impact on the soil microbial community than a single application of glyphosate. Experiments were conducted to study the effect of one, two, three, four or five applications of glyphosate on soil microbial community composition and glyphosate mineralization and distribution of ¹⁴C residues in soil. RESULTS: Fatty acid methyl esters (FAMEs) common to gram‐negative bacteria were present in higher concentrations following five applications relative to one, two, three or four applications both 7 and 14 days after application (DAA). Additionally, sequencing of 16S rRNA bacterial genes indicated that the abundance of the gram‐negative Burkholderia spp. was increased following the application of glyphosate. The cumulative percentage ¹⁴C mineralized 14 DAA was reduced when glyphosate was applied 4 or 5 times relative to the amount of ¹⁴C mineralized following one, two or three applications. Incorporation of ¹⁴C residues into soil microbial biomass was greater following five glyphosate applications than following the first application 3 and 7 DAA. CONCLUSION: These studies suggest that the changes in the dissipation or distribution of glyphosate following repeated applications of glyphosate may be related to shifts in the soil microbial community composition. Copyright © 2009 Society of Chemical Industry     

Behaviour of trifloxystrobin and tebuconazole on grapes under semi‐arid tropical climatic conditions

BACKGROUND: A mixture of trifloxystrobin and tebuconazole is excellent in controlling both powdery and downy mildew of grapes. The objective of the present work was to study the behaviour of trifloxystrobin and tebuconazole on grape berries and soil following treatment with Nativo 75 WG, a formulation containing both fungicides (trifloxystrobin 250 + tebuconazole 500 g kg^?1). This study was carried out for planned registration of this mixture for use on grapes in India. RESULTS: Initial residue deposits of trifloxystrobin and tebuconazole on grapes were below their maximum residue limit (MRL) of 0.5 and 2 mg kg^?1, respectively, when Nativo 75 WG was applied at the recommended dose of 175 g product ha^?1. The residues dissipated gradually to 0.02 and 0.05 mg kg^?1 by 30 days, and were below the quantifiable limit of 0.01 mg kg^?1 at the time of harvest (60 days after the last treatment). Trifloxystrobin and tebuconazole dissipated at a pre‐harvest interval (PHI) of 36 and 34 days, respectively, from the recommended treatment dose. The acid metabolite of trifloxystrobin, CGA 321 113, was not detected in grape berries at any point in time. Soil at harvest was free of any pesticide residues. CONCLUSION: Residue levels of both trifloxystrobin and tebuconazole were below MRLs when grapes were harvested 30 days after the last of four applications of 175 g product ha^?1 (trifloxystrobin 44 g AI ha^?1, tebuconazole 88 g AI ha^?1) under the semi‐arid tropical climatic conditions of India. Copyright © 2010 Society of Chemical Industry     

The estimation of residue levels of promacyl and its metabolites in beef tissue and fat by high-performance liquid chromatography with electrochemical detection

A method is described for the estimation of residues of the carbamate insecticide promacyl [5-methyl-m-cumenyl butyryl(methyl)carbamate] and its metabolites that are hydrolysable to isothymol (m-cymen-5-ol), using high-performance liquid chromatography with electrochemical detection to determine the isothymol. Clean-up of samples relied on the steam volatility of phenols. Recoveries at the 0.1 mg kg^?1 level varied from 72–88% for fat tissue and 81–91% for liver. The limits of detection were found to be 0.01 mg kg^?1 for and 0.02 mg kg^?1 for liver. A comparative study of the chromatography of sample extracts using both ultraviolet detection and electrochemical detection showed a substantial decrease in the level of interfering co-eluates in the latter method. A field trial, involving a single spray application of the formulated acaricide on milking cattle, revealed residues in the butter fat comparable with those found in a previous investigation.     

Residues of the algicide endothal in water,soil and rice,after paddy field applications

In order to obtain residue data from the application of the algicide endothal in Italian rice paddy fields, two experiments were carried out using a 50 g kg^?1 granular formulation in a small pond and the same granular and two liquid formulations in actual paddy fields of the Italian rice growing area. Endothal decay in the pond water was very rapid, reaching residue levels of 0·01-1·02 mg litre^?1 in two days and 0·004-0·01 mg litre^?1 at the third day. The muddy soil of the pond was free from measurable endothal residues( <0·02 mg kg^?1). In the paddy-field waters, the endothal decay was slower, with an average half-life time of 3·3 days, independently of the type of formulation. The actual residues in water after 6 days ranged from 0·3 to 1·3 mg litre^?1 according to the initial amount of product applied, and, consequently, to the initial concentration in water. Rice samples collected at the normal harvest time from the two paddy fields, treated with three different formulations, showed no endothal residue at the minimum detectable level of 0·01 mg kg^?1.     

Untersuchungen zum Einfluss einer Pflanzenschutzmittelspritzfolge auf das Rückstandsverhalten von Terbutryn und die mikrobielle Aktivität im Boden. Teil II. Beeinflussung der mikrobiellen Aktivität

Studies on the effect of a pesticide spray sequence on the behaviour of terbutryn residues and on soil microbial activity. Part II. Influence on microbial activity In laboratory incubation experiments (at 10 and 20°C and 30 and 60% soil water-holding capacity) soil microbial activities (dehydrogenase, respiration after glucose amendment and nitrogen transformations) were scarcely affected by 20·9 and 28·0 mg kg^?1, respectively, of terbutryn in two soils of different sorption properties. In contrast, dinosebacetate, alone or mixed with terbulryn, triadimefon or parathion, inhibited dehydrogenase activity and respiration even at a low rate of application (2·87 mg kg^?1). Following application of a 10 times higher rate to a highly adsorbent soil there was an initial inhibition of nitrification followed by an enhanced rate of nitrogen mineralization. Triadimefon and parathion, alone and in combination with other pesticides, caused both stimulation and inhibition of microbial activity; the reason is not clear. The effects on dehydrogenase and respiration were confirmed in field experiments. Dehydrogenase activity was the most sensitive and so could be a useful test for the side-effects of pesticides on soil micro-organisms. Additional work on nitrogen transformations is needed to interpret the results.     

Comparative purification methods for determination of triadimenol residues in plant material

Two procedures are described for the determination of residues of triadimenol and compared on cereal material. After extraction, purification is carried out by Florisil column chromatography in method I and by semi-preparative High-Performance Liquid Chromatography in method II. Triadimenol residues are quantified by gas chromatography with a thermoionic detector. With method I, interference was observed but not with method II. This specific procedure has been tested on other plant materials. Recoveries in the range of 90–98% indicate that this procedure is suitable for residue analysis of this fungicide with detection limits of 0·008 mg kg^?1 in wheat grains, 0·03 mg kg^?1 in wheat straw and 0·004–0·008 mg kg^?1 in other plants. Maximum residue limits in France are: 0·1 mg kg^?1 in grain, 2·0 mg kg^?1 in straw and 1·0 mg kg^?1 in other vegetables and fruit.     

Degradation of mecoprop at different concentrations in surface and sub-surface soil

Biodegradation of [ring-¹⁴C] mecoprop (2-(4-chloro-2-methylphenoxy)propionic acid) was determined in surface and sub-surface soil at concentrations of 0·0005, 0·05, 0·5, 5, 50, 500, 5000 and 25000 mg kg^-1. The kinetics of mineralisation were evaluated from the mineralisation rates as a function of time and by non-linear regression analysis. In the sub-surface soil, degradation was 6–8 times slower than in surface soil, but the shape of the curves was the same in both layers. At concentrations between 0·0005 and 0·5 mg kg^-1, in both surface and sub-surface soil, degradation was initially zero-order followed by first-order kinetics. At 5 to 500 mg kg^-1 in surface soil and 5 to 50 mg kg^-1 in sub-surface soil the degradation rate was initially either constant or decreasing followed by exponential degradation indicating increasing populations of mecoprop decomposers in the soil. At 5000 and 25000 mg kg^-1 in the surface soil and at 500, 5000 and 25000 mg kg^-1 in the sub-surface soil, the degradation was negligible, as determined by the percentage [¹⁴C] carbon dioxide evolved. By non-linear regression, the three-half order model was found to describe the mineralisation. © 1998 SCI     

Effects of pesticides on 1,3-β-glucanase and urease activities in soil in the presence and absence of fertilisers,lime and organic materials

The effect of four herbicides (2, 4-D, di-allate, benzoylprop-ethyl and glyphosate) and one insecticide (malathion) on 1, 3-β-glucanase and urease activities in soil was investigated in the laboratory. Concentrations equivalent to five times the recommended field application rates of the pesticides, applied as their formulations, had no effect on the activity of either enzyme, under a variety of incubation conditions, which included various moisture regimes and soil treatments. The soil enzyme systems could only be disrupted by unrealistically high dosage rates of the active ingredients (0.1–1.0 g kg^?1 of soil), Thus 1, 3-β-glucanase activity was enhanced by 2, 4-D, inhibited by di-allate, benzoylprop-ethyl and malathion, but unaffected by glyphosate; whereas urease activity was inhibited by 2, 4-D, but unaffected by di-allate, benzoylprop-ethyl and glyphosate.